Treated textile material and method of producing the same



Unite TREATED TEXTILE MATEREAL AND METHGD F PRODUCRNG THE SAME Fred H.Steiger, Philadelphia, and James P. Shelley, Drexel Hill, Pa., assignorsto Rohm & Haas Company, Philadelphia, 1%., a corporation of Delaware NoDrawing. Application December 17, 1954, Serial No. 476,068

23 Claims. (Cl. 117-1383) HzNCOOCHzCHzOCHzCHzOCON H2 with formaldehydeand either with or without methanol. This treatment may be effected forvarious purposes for imparting a variety of properties to the textilematerials as will appear hereinafter. One particularly important aspectof the invention is the treatment of plastic textile materials,especially those comprising thermoplastic fibers or yarns, to impartimproved qualities in respect to stiffness, appearance, drape and feel.

The primary object of the present invention is to provide novel textilematerials. An ancillary object is to provide textile fabrics which areimproved in respect to various properties such as stiffness and hand andparticularly in respect to resistance to change in such properties onwashing under conventional conditions. Another object is to provideprocesses for treating textile materials to impart improved propertiesthereto. Other objects and advantages will be apparent from thedescription thereof hereinafter.

In general, textile materials are improved in accord ance with thepresent invention by the application of certain novel resin-formingreaction products of formaldehyde with the dicarbamate of diethyleneglycol and subsequently drying and curing the reaction product toconvert it to an insoluble condition by means of heat and catalyst. Thepurposes and the properties obtained may be various and depend onvarious factors, such as the amount of the resin added to a fabric,whether reaction occurs between the resin and fabric, and the manner orextent of distribution on the textile material as well as others as willbe explained in more detail hereinafter.

The composition applied to the textile material in accordance with theinvention is a special film-forming condensate of the dicaroamate ofdiethylene glycol with formaldehyde and with or without methanol in anaqueous solution or dispersion. These special condensates, which arehereinafter generally referred to simply as dicarbamate condensates, areobtainable only under certain reaction conditions and are the subjectmatter of copending application Serial No. 437,268, filed June 16, 1954,and now Patent No. 2,774,746. The required conditions include the use ofa narrow pH range of 2.3 to 3.5 during the reaction of the formaldehydewith the dicarbamate in aqueous medium. The concentration of theformaldehyde and dicarbamate in the initial reaction medium should bebetween 50% and 85% by weight of the total weight of the reactionmedium. The molar ratio between the formaldehyde and the dicarbamate inthe reaction medium at the start of the reaction must be between 2:1 and35:1. formaldehyde to dicarbamate is between 2.5 and 3 moles offormaldehyde to one of the carbamate. The temperature may vary from 70C. to the boiling point of the reaction medium which may be as high as105 to 110 C. at normal atmospheric pressure, or higher when the Statesatent O The preferred mole ratio of reaction is carried out underpressures above normal atmospheric pressure or in the presence of othersolvents which are inert to the reaction, for example,dimethylfonnamide.

Under the conditions just outlined, the reaction is carried out untilthe condensation product has a viscosity, as determined in a solution inwater of a 60% solids concentration at 25 C., of at least 2 poises butnot over 25 poises. Preferably the condensate when tested under theseconditions has a viscosity between 6 and 20 poises. The solids referredto is determined by diluting a sample of the aqueous condensate with anequal weight of water, weighing the residue of a portion (0.6 to 0.8gram) after heating minutes at 125 C. to determine the percentage ofsolids in said portion and multiplying by a factor of 2 to compensatefor the dilution. required to attain the required viscosity depends uponthe several conditions of pH, concentration, temperature and ratio offormaldehyde to dicarbamate within the ranges set out above. Dependingupon the several conditions just stated, the desired molecular weight ofthe condensation may be attained within a period of from ten minutes toeight hours or more reaction time.

The condensation may also take place in the presence of methyl alcoholwhich is believed to combine with the reactants to form methylatedderivatives. The proportion of methyl alcohol when used may be from 1 to2.5 moles per mole of dicarbamate and is preferably from 1.5 to 2 molesper mole of dicarbamate. When the condensation is effected in thepresence of methyl alcohol, it is preferred to carry out the reaction inthe lower portion making or applying them would require the use oforganic solvents.

The temperature of the reaction medium is preferably that whichcorresponds to the reflux or boiling temperature thereof which isgenerally lower when methyl alcohol is present than when the reactionmedium is simply water.

The preferred temperature when water alone is used as the solvent mediumis from 90 to C., but as pointed out hereinabove, higher temperaturesmay be employed when superatmospheric pressure is employed, whether thereaction medium contains methyl alcohol or not.

The concentration in the reaction medium when methyl alcohol is presentmay vary from 50% to 85%. When no methyl alcohol is present, theconcentration of formaldehyde and dicarbamate within the aqueous mediumis from 50% to 75% and is preferably between 60% and 70%.

After the reaction has been effected to the viscosity within the rangespecified hereinabove, the reaction medium or mass is cooled to 30 C. orlower. Preferably the cooled mass is then neutralized by the addition ofa suitable alkaline material such as a soluble oxide, hydroxide, orcarbonate, and preferably with the hydroxide of ammonium or an alkalimetal such as sodium or potassium. After neutralization with sodium orpotassium hydroxide, the reaction mass still shows infinite watertolerance. When neutralized with ammonium hydroxide, however, thosereaction masses, in which the' higher viscosity is attained within therange specified, sometimes have less than infinite water tolerance, butin of water.

The time hydroxide can be diluted with from 30 to 70 cc. of water atnormal room temperature without forming distinct layers. However, evenin those cases where neutralization reduces the water-compatibility ortolerance, the material recovers infinite tolerance to water uponreacidification.

The reaction between the dicarbarnate and formaldehyde may be carriedout generally as follows: The dicarbamate is introduced into aqueous 37%formaldehyde producing various concentrations depending upon the ratioof formaldehyde to the carbamate, the initial concentration being about64% when the mole ratio of formaldehyde to dicarbamate is 3.0:1. Thedispersion on heating becomes a clear solution and it is preferred tostrip Water by distillation to bring the concentration to about 60%reaction product at which time sulfuric acid or other catalysts areadded to reduce the pH to a value from 2.3 to 3.5, preferably from 2.3to 2.8 if methanol is present or from 2.5 to 3.0 if methanol is absent.At this point, the viscosity of the reaction medium is generally about/2 to 1 poise (at 65% concentration). It should be understood that theacid may be added before stripping, but this is not preferred. Thereaction mass is heated to condense the formaldehyde dicarbamatereaction product to a viscosity of at least 2 poises at 60%concentration in water at 25 C. The reaction mass at this time hasinfinite water tolerance and retains it on partial or completeneutralization with sodium hydroxide or potassium hydroxide to a pH of 5to 7.5.

The resulting reaction mass may have a concentration of the condensateof 50% to 70% or more and it may be used directly for coating orfilm-forming purposes. When so used reasonably promptly, neutralizationmay be omitted. Thus the unneutralized condensate formed withoutmethanol can be used within about 12 to 24 hours whereas those formedwith methanol can be used within one week to several months depending onthe degree of condensation without encountering troublesome gelling.

If reasonably prompt use is not desired, the reaction mass should betreated with an alkaline material to raise the pH to a value of 5 to 7,preferably 6.0 to 6.5. It is preferred to avoid raising the pH above 6.5because of the tendency for too much salt to be formed so that the salttends to crystallize out of the reaction mass on standing. The partiallyor completely neutralized reaction mass may be stored indefinitelyWithout dilution and transported to the point of application where anacid catalyst may be introduced just before it is applied for theformation of coatings or films on the textile materials. A strong acidcatalyst such as sulfuric acid, toluenesulfonic acids, ethanesulfonicacid, ammonium phosphate, ammonium thiocyanate, hydrochloric or otheracid salts of a hydroxy aliphatic amine includingZ-methyl-Z-aminol-propanol, 2-methyl-2-amino-1,3-propandiol, tris(hydroxymethyl)-aminomethane, 2-phenyl-2-amino-l-propanol, 2-methyl-2-amino-l-pentanol, 2--aminobutanol, triethanolamine,2-amino-2-ethyl-l-butanol, ammonium chloride, pyridine hydrochloride,and benzyldimethylamine oxalate may be used. The amine salts arewatersoluble latent catalysts substantially neutral at ordinarytemperature which dissociate into volatile components one of which isacidic at the elevated temperatures used for baking and curing, so thatthe catalyst after exerting its accelerating effect is automaticallydischarged from the mass during the heating stage. The amount ofcatalyst used may be from 0.2% to 6% or more by Weight based on thetotal weight of the dispersion, and is preferably about /z% to 1%.

"Because of the water-compatibility of the reaction mass, it may bediluted to any desired extent before application merely by the additionof water.

Besides the introduction of an acid catalyst to accelerate theinsolubilization of coatings, films or other products obtained from thecondensate, various materials may be added for other purposes. Forexample, surface-active agents of anionic, non-ionic, or cationic typemay be introduced to improve the flow and make the coating or film moreuniform especially when the compositions are used for making continuouscoatings on textile materials. Examples of non-ionic surface-activeagents include polyethylene oxide derivatives of phenol, of alkylphenols having 6 to 18 carbon atoms in the alkyl substituent, of higherfatty acids having from 8 to 18 carbon atoms, of higher fatty alcoholsor mercaptans having from 8 to 18 carbon atoms, of long chain aliphaticamides having from 8 to 18 carbon atoms, of long chain fatty amineshaving from 8 to 18 carbon atoms, such derivatives containing from 10 to50 or more oxyethylene units per molecule. Besides the non-ionicsurface-active agents just mentioned, anionic types such as laurylalcohol sulfate, sodium dioctyl sulfosuccinate, the sodium salt ofisopropyl naphthalenesulfonic acid, or cationic agents such as laurylpyridinium chloride may be employed. The proportion of surface-activeagent may be from 0.01 to 3% of the weight of the condensate therein.

If desired, a volatile non-aqueous solvent may be added. Preferably, anysuch additional solvent is water-soluble, such as ethanol, propanol,isopropanol, and t-butanol.

The coatings may be clear and colorless when formed without the additionof dyes or pigments, or they may be colored by the introduction ofpigments or dyes, such as titanium oxide, lithopone, carbon black,ultramine blue or the like.

After the films or coatings are formed from the aqueous condensatecontaining the catalysts with or without other materials, they are driedand hardened by heating at temperatures of about 180 F. to 350 F. orhigher.

The aqueous compositions comprising the resin-forming dicarbamatecondensate have the advantage during their application of not requiringspecial precautions to avoid the danger of fire or toxic effects on theoperators. They require no equipment for solvent recovery and water isall that is needed to wash off residue left on the quipment. They arealso dilutable to lower concentrations so that they may be shipped as ahighly concentrated aqueous composition and then diluted, especially forsuch textile applications as sizing, dressing and/or stiffening variousfabrics, such as nylon, rayon, Orion, Dacron, and the like. Thosecompositions which are derived from reaction media comprising methanolhave the additional advantages of being substantially free from odor andproducing somewhat greater flexibility in the final water-insolubilizingfilm or coating.

Depending upon the results desired, the aqueous dispersions of theresin-forming dicarbamate condensates may be applied at a concentrationof 1% to of the resin-forming condensate in the dispersion. Generally,the pick-up on the textile material may be between 25% and 50% and mostcommonly about 30%of the concentration in the aqueous dispersion whenapplied to hydrophobic materials. On hydrophilic materials, such as ofcellulosic types, the pick-up may be as high as to The application ofabout /2 to 1% by weight on the weight of a textile fabric such as awoven or knitted fabric provides a slight modification of hand andantislip properties; that is, there is imparted to the fabric aresistance to relative displacements of the yarns with respect to eachother during handling or wear. The application of 1% to 35% on theWeight of the fabric imparts a stiffness thereto in proportion to theamount deposited. This is desirable in the modification of fabrics ofmany materials and especially of polyamides, such as nylon, polyesterssuch as Dacron (polyethylene terephthalate), cellulose esters such ascellulose acetate (or the primary or triacetate type and also of thesecondary acetone-soluble type), and polyvinyl resin yars such as Orlonand other polyacrylonitrile fabrics comprising fibers or filamentsformed of acrylonitrile polymers or copolytners containing at least 80%by weight of acrylonitrile polymerized in the molecule. Such plasticfabric materials asoases I frequently have excessive softness andsleaziness which is overcome by the application of the condensates ofthe present invention. Generally, 4% to 5% by weight on the weight ofthe textile material of the dicarbamate condensate is preferred for thestiffening of dress materials, such as womens summer dresses and mensshirting materials and especially open weave summer shirts. Somewhathigher proportions, preferably 8% to 10%, may be used for the stiffeningof foraminous or netted shoe cloths of netted or woven charactercomprising fibers, filaments or yarns of the above-mentioned plasticmaterials. Other materials that maybe improved by the stiffening actionimparted by the resins of the present invention include ladiesundergarments and petticoats, netting (either knitted or woven), such asmaterials used in making ornaments or decorations for evening gowns andso on. It has been found also that the application of the dicarbamatecondensates to certain plastic materials and particularly nylon renderssuch treated materials more resistant to heat. Thus, fabrics of nylonwhich are sub jected to heat during their use, such as ironing boardcovers, quickly lose their strength. However, nylon fa- 1 brics treatedwith resins of the present invention maintain their strength even afterprolonged use under heat even under such severe conditions as areencountered during ironing.

The dicarbamate condensates are applicable to yarns as a loom finish.The application of 3% to 10% of the ments, yarns or fabrics of certainmaterials, such as rayon,

cotton, proteinaceous fibers such as of casein and the like tends toreduce shrinkage on subsequent washing and thereby imparts dimensionalstability.

The dicarbamate resin condensate may also be incorporated in fibrousstructuresof matted character, such as felt-like mats or bats comprisingfibers of any type whatsoever including mineral fibers such as thoseformed of glass or siliceous material known asmineral wools. For thispurpose, the fibers may be dispersed into an air stream and thedispersion of resin-forming condensate may be sprayed on to the fibersas they are conveyed in such stream to a point of deposition where theyare laid in haphazard disposition and subsequently heated to effectdrying and curing of the condensate deposit and thereby binding thefibers together. For producing this type of product when glass fibers ormineral fibers are involved, the condensate spray may be directedagainst the fibers in close proximity to their point of initialformation by the impingement of a gaseous stream, such as of air orsteam, against a stream of molten glass or the like.

As mentioned above, the aqueous dispersion of the resin-formingdicarbamate condensate may contain from 1% to 90% by weight of thecondensate, depending upon the particular purpose for which thecondensate is to be applied and the amount that is to be'deposited onthe textile material. A concentration approaching 90% is generallynecessary to obtain a heavy deposit of to on the weight of the textilematerial, whereas a concentration of 1% is adequate to apply about /a%to /2% of the condensate on the textile material. Intermediateconcentrations are used to provide intermediate deposit weights on thetextile material. The condensate dispersion may be applied to thetextile material by spraying, padding, by rolls, brush or any otherconventional device. Generally application is made at room temperaturethough somewhat elevated temperatures or lower temperatures may beemployed if desired in eertaincases.

The dispersion of condensate should contain a catalyst such as ammoniumchloride, an amine salt or any other of the catalysts mentionedhereinabove. As pointed out hereinbefore, the catalyst is preferablyadded shortly before the dispersion is to be used.

After the dispersion of condensate is applied to th textile material, itis dried. This may be merely drying in air or it may be effected atelevated temperatures, such as from 180 F. to 240 F. or even higher.

The condensate may then'be converted to an insoluble condition byprolonging the drying at temperatures of 180 F. to 240 F. or preferablyby heating for a short period at elevated temperatures. For example,insolubilization may be effected at temperatures of 300 F. to 450 F. orhigher for periods of time whose length varies inversely with the degreeof temperature from about ten minutes at the lower temperatures to aboutfive seconds at the higher temperature mentioned. In all cases, thetemperature should not be so high or the time prolonged to such anextent as to cause decomposition of the material composing the fabric orother textile.

As compared to such resin-forming condensates as those ofurea-formaldehyde and melamine-formaldehyde which have heretoforebeenused for the stiffening of plastic materials, such as nylon, thedicarbamate condensates have several advantages. Generally, they producea fuller hand than can be obtained from a ureaformaldehyde andmelamine-formaldehyde is the lower tendency of the former treatedfabrics to propagate flame.

The dicarbamate condensates also show less loss after washingparticularly on such materials as Orlon and Dacron. Whereas aurea-formaldehyde resin heretofore used for stiffening Orlon and Dacronshows only 55% and 67% retention on those respective fabrics afterwashing for one hour at the boil in water containing 0.1% of sodiumtetraphosphate and 0.2% of Ivory soap and Orlon and Dacron fabricscarrying melamine-formaldehyde show only 60% and 56% respectively afterwashing. Orlon and Dacron fabrics carrying dicarbamate condensates showa retention of 70% and 86% respectively after such a wash.

In the following examples, which are illustrative of the presentinvention, the glass electrode (G. E.) pH was always determined on a 5.0g. sample of the batch which had been diluted to about 10% solids with25.0 ml. of distilled water. In the following examples where stiffnessis determined, a Gurley stiffness tester was employed and the valuesgiven represent milligrams required to bend a standard sample of 1" by3" dimension.

EXAMPLE 1 Dithylene glycol dicarbamate (480 grams or 2.5 moles) wascharged to a one liter flask containing 613 grams of aqueous 36.7%formaldehyde (7.5 moles HCHO). The mixture was heated and when itcleared at about C. sulfuric acid was added to lower the pH to about3.3. Heating continued to reflux (starting about 102 C.). Refluxing wascontinued until a Gardner-Holdt viscosity of T+ was attained at a solidsconcentration of 68%. At this point the dispersion had water toleranceand had a pH of 2.8. Caustic soda was added to adjust the pH to about 6to 7 and about 9.2 grams of a polyethylene oxide derivative of an octylphenol containing about 10 oxyethylene units was added.

The dispersion was then diluted with water to a 12.5

of dispersion) of ammonium chloride was added. In a Another importantcharacteristic of the fabrics treated with the dicarbamate condensatesas i r compared with those treated with condensates of urea- I padarranged for two dips and two nips in squeeze rolls, the above 12.5%aqueous dispersion of the resin-coridensatewas applied to a nylontaffeta, a Dacron shirting fabric, an Orlon'shirting' fabric and acellulose acetate satin. After drying the treated fabrics in air, thecondensate was insolubilized by heatin'g'at 300 F. for ten minutes.The'fabrics were'thenconditioned at 70 F. and 65% relative humidity. Thefabrics'were tested for stiffness and then all exceptthe acetate weresubjected to a Wash at the boil for one hour in an aqueous solution of0.1% sodium te'trapliosphate, 0.2% of Ivory soap. After the wash thestiffness was againtested. The following table gives the rcsults'of thestiffness tests.

Table 1 Nylon Orion Dacron Acetate wt iia Washed wit d Washed wideWashed wiiiia EXAMPLE 2 A nylontafieta was padded as before with aseries of resin condensates preparedas in Example 1 except that eachdispersion 'was finally diluted to solids concentrations of andrespectively. To each dispersion, there was added /2% of ammoniumchloride based on the total weight of the dispersion.

The fabrics after drying, curing and conditioning as in Example 1 weretested for stiffness, then washed as in Example 1 and again tested forstiffness. Table II summarizes the results obtained after application ofthe different concentrations of resin-dispersion and comparing it with acontrol using-water.

EXAMPLE 3 Samples of a Dacron fabric were treated with the severalcatalyzed dispersions of condensate prepared as in Example 2 having 5%,10%, 15%, 20%, and 25% concentrations respectively. Similarly catalyzedureaformaldehyde and melamine-formaldehyde condensates havingcorresponding concentrations were also applied to similar samples of theDacron fabric. The treated samples Were dried, cured and conditioned asin Example 1. They were then tested for stiffness, washed as in Example1 and againtested for stiffness. Table Hi summarizes the results ofthese tests. The symbols DGC-F refers to the condensates of the presentinvention; U-F to the urea-formaldehyde; and M-F Disp. Con.

W. V Unw. W. Unw. W.

8 EXAMPLE 4 .Dispersions of the diethylene glycoldicarbamateformaldehyde condensate preparedas in Example 1 and ofurea-formaldehyde and melamine-formaldehyde were applied, at solidsconcentrations of 5% and 15% respectively and inieach case containing0.5% ammonium chloride on the weight ofthe dispersion, to nylon taffetasinthe manner described in Example 1. The treated fabrics were air-dried,cured and conditioned as in Example 1. Strips 1" wide by 8" in lengthwere then subjected to burning tests. Other portions'of the fabricwere-washed as in the manner described in Example 1 and againafter-drying were tested for flammability. The

results are'tabulated in Table IV, wherein the values Table IV Unwashed,Washed,

inches inches 2 4 5 co 3 w 3 co ED 3 2 EXAMPLE 5 There are charged intoa reaction vessel 1,152 grams of diethylcne glycol dica'rbamate (6moles) and 983 grams of an aqueous solution containing of formaldehyde,35% of methanol and 10% of water. This provides 18 moles of formaldehydeand approximately 10.6 moles of methanol. The mixture is heated and whenit clears at about C. 100 grams of phosphoric acid is added to adjustthe pH to about 2.6. The mixture is then refluxed. After several hours,200 grams of water is added to reduce the viscosity and 70 grams of a40% solution of paratoluenesulfonic acid in isopropyl alcohol is addedto reduce the pH to a value of 2.6. After additional refluxing theviscosity increased to U (Gardner-Holdt) and 200 grams of water wereadded to reduce it. Refluxing continued until a viscosity of U wasattained. This completed the reaction and 400 grams of Water were addedto reduce the viscosity to G. A 50% solution of sodium hydroxide wasadded until the pH Was raised to about 6%.. Then water was added toreduce the dispersion to a 10% solids content and /2% of ammoniumchloride was added (based on the Weight of the dispersion).

The 10% dispersion of condensate thereby obtained Was applied to a nylontaffeta, which was then dried, cured and conditioned all as inExample 1. Thetensile strength in pounds (at break) was measured by aScott testing machine on a strip 6" long in the warp direction which wasfrayed in conventional manner to a 1" Width to assure that the samenumber of Warp yarns extended through the entire length of the strip.Similar strips of nylon taffeta were prepared except that they weretreated with 10% dispersions of urea-formaldehyde andmelamine-formaldehyde condensates respectively each containing /z% of anacidic catalyst; ammonium chloride being used in the case ofurea-formaldehyde and a di ammonium phosphate being the catalyst used inthe case of the melamine-formaldehyde. strips thus obtained were testedfor tensile strength as in the case of thestrip treated with the.diethylene glycol The dried and cured escapes dicarbamateformaldehydecondensate. Another set of similarly treated nylon taffeta strips, whichhad been cured in the same manner, was subjected to a heat treatment forten minutes at 400 F. and the tensile strength measured thereafter.Table V summarizes'the results of these tensile tests before and afterthe heat treatment.

(a) Diethylene glycol dicarbamate (480 grams or 2.5 moles) was chargedto a one-liter flask containing 613.0 grams of aqueous 36.7%formaldehyde (7.5 moles HCHO). The mixture was heated with stirring toreflux (102 C.) and held at this temperature for 15 minutes in order toallow time for some reaction to take place between formaldehyde and thecarbamate before starting to strip the batch. Then the heat was shut olfwhile the apparatus was arranged for distillation (ca 10 min.) afterwhich heating was resumed and 63.0 grams of aqueous distillate wasdistilled from the reaction mixture (batch temp. was 104 C. at thispoint). Heat was again shut off while the apparatus was arranged fortotal reflux (about 15 minutes). When heating was then resumed, thebatch temperature was 90 C. and the pH of the batch was adjusted to 3.0(G. E.) with 2.4 ml. of 50% aqueous H2804 and the batch (having about60% solids content) was sampled for viscosity. The viscosity at thispoint was A on the Gardner-Holdt scale at 25 C. or slightly less than /2poise at 25 C.

Further polymerization of the batch was effected by continuing to heatat reflux until the viscosity reached a value of D on the Gardner-Holdtscale. At this point, about /3 of the batch was removed providing adispersion hereinafter referred to as dispersion A having a solidsconcentration of about 60%. Refluxing of the original batch continueduntil the viscosity reached a value of At this point, about one-half ofthe remaining batch was removed and it is hereinafter referred to asresin dispersion B. It had a solids concentration of about 56.3%. Theremainder was refluxed further until it reached a viscosity of M atabout 52% solids. This will be referred to as resin dispersion C.

(b) A mixture of 1,080 grams of aqueous 36.5% formaldehyde, 1,920 gramsmoles) of diethylene glycol dicarbamate, 915 grams of a solutioncontaining 55% of formaldehyde, 35% methanol and 10% water, and 475grams of water was charged into a reaction vessel and heated. When thetemperature reached about 70 C., the reaction mass cleared and 10 gramsof a 50% aqueous sulfuric acid was added to lower the pH to 3.3 and heatwas continued to reflux (starting at about 88 C.). After about 8 hoursreflux the reaction mass had a solids concentration of about 55.5% and aGardner- Holdt viscosity of about C. Twelve hundred grams of thereaction mass was removed and this removed portion will hereinafter bereferred to as resin dispersion D.

About one gram of 50% sulfuric acid was added to the remaining reactionmass and refluxing thereof was continued until the viscosity reached M+at a 56% solids concentration. At this time, 1,200 grams of the reactionmass were removed and will hereinafter be referred to 10 as resindispersion E. The remaining reaction mass was further refluxed until aviscosity of V- was attained at a 60% solids concentration and thisremaining portion will hereinafter be referred to as resin dispersion F.

(c) A mixture of 1,920 grams (10 moles) of diethylene glycoldicarbamate, 1,640 grams of an aqueous solution containing 55%formaldehyde (30 moles), 35% meth anol and 10% water, 67 grams ofadditional methanol (providing a total of 20 moles of methanol), and 760grams of additional water were mixed in a reaction vessel and heated.The mass cleared at about 75 C. at which point 6 grams of 50% sulfuricacid was added to lower the pH to 3.3 Heating was continued to bring themass to reflux which started at about 95 C., and at this stage anadditional one gram of the 50% sulfuric acid was added to maintain thepH at 3.3. Refluxing was continued until the mass attained a viscosityof C+ at a concentration of 59.2% solids. At this point, 1,200 grams ofthe dispersion was removed and will be hereinafter referred to as resindispersion G. About eight grams of 50% sulfuric acid was added to theremainder to lower its pH to 3.3 and refluxing continued. The refluxingtemperature lowered to about C. during the process until a viscosity ofM is attained at a solids concentration of 57.7%. A 1,200 gram portionof the mass was removed and this portion will be hereinafter referred toas resin dispersion H.

Then about lgram of the 50% sulfuric acid was added to the remainingreaction mass amounting to approximately 1,200 grams which was refluxedfor a further period of time until the viscosity reached a value of T+at a concentration of 57.9% solids. This remaining portion ishereinafter referred to as resin dispersion I.

(d) The several resin dispersions of parts (a), (b), and (c) hereofrepresent three diethylene glycol dicarbamate-formaldehyde condensatetypes; that in part (a containing no methanol and being divided intodispersions containing condensates carried to different degrees ofcondensation; that in part (b) obtained from a mixture containing about1 mole of methanol per mole of dicarbamate divided into dispersionscontaining condensates of different degrees of condensation; and that inpart (0) being a condensate obtained from a mixture containing about twomoles of methanol per mole of dicarbamate and being divided into threeportions, each having a different degree of condensation.

Each of the resin dispersions thus obtained is neutralized to a pHbetween about 5 and 6.5 with a 50% aqueous solution of sodium hydroxide.To portions of each of the dispersions water is added to reduce thesolids concentration to 25% and to other portions water is added toreduce the solids concentration to 7.5 Then there is added to each ofthe resulting dispersions, 0.5% of ammonium chloride (on the weight ofdispersion).

Condensates of urea-formaldehyde and melamineformaldehyde were alsoprepared in concentrations of 25% and 7.5% in aqueous dispersions andprovided with /2% of ammonium chloride as a catalyst (based on the totalweight of dispersion).

(e) The 18 dispersion of dicarbarnate-forma-ldehyde condensates, the 2dispersions of urea-formaldehyde condensates and the 2 ofmelamine-formaledlhyde were then applied to nylon, Orlon and Dacronfabrics in a pad by the procedure of Example 1. After drying, curing andconditioning as in Example 1, the samples of the several treated fabricswere tested for stiffness. Additional samples were subjected to the washas in Example 1 and then again tested for stiffness. Table VI summarizesthe results of these tests. Under each fabric designation the thirdcolumn with the percent sign at the top represents percentage retentionof stiffness after washing.

UN W cent UN W cent UN W cent 7.5% Concentration Resin Dispersion:

12 11 91 32 8 25 25 13 52 13 77 34 13 38 29 12 42 8 7 87 32 28 87 23 2191 9 7 78 34 29 85 25 19 76 9 8 89 34 26 76 25 22 88 10 9' 90 32 26 8422 16 73 11 9 81 36 26 72 25 .21 84 9 7 78 33 25 76 24' 18 75 7 7 100 2825 89 19 17 90 11 9 81 32 22 69 19 17 90 I 8 9 110 32 26 81 18 90Concentration Resin Dispersion:

The stiffness test on untreated samples run approximately 3 for nylon, 8for Orlon, and 15 for Dacron.

- It is to be understood that changes and variations may be made withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

. We claim:

1. A method of modifying a textile material comprising treating it withan aqueous dispersion containing dispersed therein 1% to 90% of awater-soluble high molecular weight condensate obtained by reacting at apH between 2.3 and 3.5 a mixture comprising the dicarbamate ofdiethylene glycol and formaldehyde, in which the molar ratio offormaldehyde to the dicarbamate is from 2.5:1 to 3.0:1, said condensatehaving a viscosity, at a concentration of 60% in water at 25 C., of 2 to25 poises, said composition containing 1% to 6% by weight of an acidcatalyst, drying and heating the treated material at a temperature of atleast 180 F. to 350 F.

2. An article of manufacture comprising a woven textile fabric carryingthereon 3% to 10%, based on the weight of the material, of an insolubledeposit of a condensate of the dicarbamate of diethylene glycol andformaldehyde, said article being the product of the method defined inclaim 1.

3. A method of modifying a textile material comprising treating it withan aqueous dispersion containing dispersed therein 1% to 90% of awater-soluble high molecular weight condensate obtained by reacting at apH between 2.3 and 3.5 a mixture comprising methanol, the dicarbarnateof diethylene glycol and formaldehyde in which the molar ratio offormaldehyde to the dicarbamate is from 2:1 to 35:1 and that of themethanol to the dicarbamate is from 1:1 to 2.5 :1, said condensatehaving a viscosity, at a concentration of 60% in water at 25 C., of 2 to25 poises, said composition containing 1% to 6% by weight of an acidcatalyst, drying and heating the treated material at a temperature of atleast 180 F. to 350 F.

'4. An article of manufacture comprising a textile ma terial carryingthereon /z% to 35%, based on the weight of the material, of an insolubledeposit formed from a condensate obtained by reacting at a pH between2.3 and 3.5 a mixture comprising the dicarbamate of diethylene glycol,formaldehyde, andmethanol, in which the molar ratio of formaldehyde todicarbamate is from 2:1 to 3.521 and that of the methanol to thedicarbamate is 1:1 to 2.5 :1, said article being the product of themethod defined in claim 3.

5. An article as defined in claim 4 in which the material is a fiber.

6. An article as defined in claim 4 in which the material is a yarn.

7. An article as defined in claim 4 in which the material is a textilefabric.

8. An article as defined in claim 4 in which the material is a textilefabric comprising yarns of polyethylene terephthalate.

9. An article as defined in claim 4 in which the material is a textilefabric comprising yarns of nylon.

10. An article as defined in claim 4 in which the material is a textilefabric comprising yarns of a polymer of acrylonitrile comprising atleast 80% acrylonitrile polymerized therein.

11. An article as defined in claim 4 in which the material is a textilefabric comprising yarns of a cellulosic material.

12. An article as defined in claim 3 in which the material is a textilefabric comprising yarns of cellulose acetate.

13. An article as defined in claim 4 in whiih the material is a textilefabric comprising yarns of rayon.

14. A method of modifying a textile material comprising treating it withan aqueous dispersion containing dispersed therein 1% to 90% of awater-soluble high molecular weight condensate obtained by reacting at apH between 2.3 and 3.5 a mixture comprising the dicarbamate ofdiethylene glycol and formaldehyde, in which the molar ratio offormaldehyde to the dicarbamate is from 2:1 to 35:1, said condensatehaving a viscosity, at a concentration of in Water at 25 C., of 2 to 25poises, said composition containing 1% and 6% by weight of an acidcatalyst, drying and heating the treated material at a temperature of atleast 180 F. to 350 F.

15. A method as defined in claim 14 in which the material is a woventextile fabric comprising fibers or filaments of polyethyleneterephthalate.

16. A method as defined in claim 14 in which the material is a woventextile fabric comprising fibers or filaments of nylon.

17. A method as defined in claim 14 in which the material is a woventextile fabric comprising fibers or filaments of cellulosic material.

18. A method as defined in claim 14 in which the material is a woventextile fabric comprising fibers or filaments of cellulose acetate.

19. A method as defined in claim 14 in which the material is a. woventextile fabric comprising fibers or filaments of rayon.

20. A method as defined in claim 14 in which the material is a woventextile fabric comprising fibers or filaments of a polymer ofacrylonitrile comprising at least acrylonitrile polymerized therein.

21. An article of manufacture comprising a textile material carryingthereon to 35%, based on the weight of the material, of an insolubledeposit of a condensate of the dicarbamate of diethylene glycol andformaldehyde, said article being the product of the method defined inclaim 14.

22. A method of modifying a textile material comprising treating it withan aqueous dispersion containing dispersed therein 1% to of awater-soluble high molecular weight condensate obtained by reacting at apH between 2.3 and 3.5 a mixture comprising methanol, the dicarbamate ofdiethylene glycol and formaldehyde, in which the molar ratio offormaldehyde to the clicarbamate is from 2.521 to 3:1 and that of themethanol to the dicarbamate is from 1.5 :1 to 2:1, said condensatehaving a viscosity, at a concentration of 60% in water at 25 C., of 2 to25 poises, said composition containing 1% to 6% by weight of an acidcatalyst, drying and heating the treated material at a temperature of atleast F. 350 F.

and 3.5 a mixture comprising the dicarbamate of di- 5 ethylene glycol,formaldehyde, and methanol, in which the molar ratio of formaldehyde todicarbamate is from 2.5 :1 to 3:1 and that of the methanol to thedicarbamate is 1.521 to 2:1, said article being the product of themethod defined in claim 22.

References Cited in the file of this patent UNITED STATES PATENTS2,518,266 Baird et al.. Aug. 8, 1950 14 Baird et a1. Aug. 8, 1950 Bairdet a1 Aug. 15, 1950 FOREIGN PATENTS Great Britain Sept. 1, 1938 FranceNov. 4, 1942 France Feb. 21, 1944

1. A METHOD OF MODIFYING A TEXTILE MATERIAL COMPRISING TREATED IT WITHAN AQUEOUS DISPERSION CONTAINING DISPERSED THEREIN 1% TO 90% OF AWATER-SOLUBLE HIGH MOLECULAR WEIGHT CONDENSATE OBATAINED BY REACTING ATA PH BETWEEN 2.3 AND 3.5 A MIXTURE COMPRISING THE DICARBAMATE OFDIETHYLENE GLYCOL AND FORMALDEHYDE, IN WHICH THE MOLAR RATIO OFFORMALDEHYDE TO THE DICARBAMATE IS FROM 2.5:1 TO 3.0.1, SAID CONDENSATEHAVING A VISCOSITY, AT A CONCENTRATION OF 60% IN WATER AT 25*C, OF 2 TO25 POISES, SAID COMPOSITION CONTAINING 1% TO 6% BY WEIGHT OF AN ACIDCATALYST, DRYING AND HEATING THE TREATED MATERIAL AT A TEMPERATURE OF ATLEAST 180*F. TO 350*F.